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United States Patent |
6,084,099
|
Hackmann
,   et al.
|
July 4, 2000
|
Preparation of N,N'-dialkylperylene-3,4,9,10-tetracarboxylic acid
diimides
Abstract
Preparation of N,N'-di(C.sub.1 -C.sub.4
alkyl)perylene-3,4,9,10-tetracarboxylic acid diimides (I) by the reaction
of perylene-3,4,9,10-tetracarboxylic acid diimide (II) with a C.sub.1
-C.sub.4 alkyl halide, in which the reaction is carried out in a
dipolar-aprotic organic solvent in the presence of an inorganic base.
Inventors:
|
Hackmann; Claus (Ludwigshafen, DE);
Acker; Michael (Heidelberg, DE);
Henning; Georg (Ludwigshafen, DE);
Mensch; Siegfried (Maxdorf, DE)
|
Assignee:
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BASF Aktiengesellschaft (Ludwigshafen, DE)
|
Appl. No.:
|
147202 |
Filed:
|
October 28, 1998 |
PCT Filed:
|
July 29, 1997
|
PCT NO:
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PCT/EP97/04101
|
371 Date:
|
October 28, 1998
|
102(e) Date:
|
October 28, 1998
|
PCT PUB.NO.:
|
WO98/06786 |
PCT PUB. Date:
|
February 19, 1998 |
Foreign Application Priority Data
| Aug 09, 1996[DE] | 196 32 204 |
Current U.S. Class: |
546/37; 546/36 |
Intern'l Class: |
C07D 471/02 |
Field of Search: |
546/36,37
|
References Cited
U.S. Patent Documents
4585878 | Apr., 1986 | Jost et al. | 548/453.
|
5017713 | May., 1991 | Kondo et al. | 552/237.
|
Foreign Patent Documents |
1 433 688 | Feb., 1966 | FR.
| |
2.027.743 | Jan., 1970 | FR.
| |
2 394 581 | Jun., 1978 | FR.
| |
276 357 | Jun., 1913 | DE.
| |
276 956 | Jun., 1928 | DE.
| |
1 272 270 | Feb., 1961 | DE.
| |
21 53 087 | Oct., 1971 | DE.
| |
27 27 484 | Jan., 1979 | DE.
| |
48-001409 | Jan., 1973 | JP.
| |
WO 96/08537 | Mar., 1996 | WO.
| |
Primary Examiner: Kumar; Shailendra
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt, P.C.
Parent Case Text
This application is a 371 of PCT/EP97/04101, filed Jul. 29, 1997.
Claims
We claim:
1. A process for the preparation of N,N'-di(C.sub.1 -C.sub.4
alkyl)perylene-3,4,9,10-tetracarboxylic acid diimides (I) by the reaction
of perylene-3,4,9,10-tetracarboxylic acid diimide (II) with a C.sub.1
-C.sub.4 alkyl halide, wherein the reaction is carried out in a
dipolar-aprotic organic solvent in the presence of an inorganic base.
2. A process as defined in claim 1, wherein the dipolar-aprotic solvent is
selected from the group consisting of a carboxamide, a lactam, a cyclic or
acyclic urea derivative, a sulfoxide, and a sulfone, and a mixture
thereof.
3. A process as defined in claim 1, wherein the dipolar-aprotic solvent is
dimethyl formamide or dimethyl acetamide.
4. A process as defined in claim 1, wherein the inorganic base is an alkali
metal salt of a weak inorganic acid.
5. A process as defined in claim 1, wherein the inorganic base is sodium or
potassium carbonate.
6. A process as defined in claim 1, wherein the alkyl halide is an alkyl
chloride.
7. A process as defined in claim 1, wherein the reaction is carried out at
from 140.degree. to 180.degree. C. under autogenous pressure.
8. A process as defined in claim 1, which is used for the preparation of
N,N'-dimethyl perylene-3,4,9,10-tetracarboxylic acid diimide (Ia).
Description
The present invention relates to a novel process for the preparation of
N,N'-di(C.sub.1 -C.sub.4) alkylperylene-3,4,9,10-tetracarboxylic acid
diimides (I) by the reaction of perylene-3,4,9,10-tetracarboxylic acid
diimide (II) with a C.sub.1 -C.sub.4 alkyl halide.
N,N'-di(C.sub.1 -C.sub.4)alkylperylene-3,4,9,10-tetracarboxylic acid
diimides (I q; referred to below as "dialkyl perylimides"), and primarily
dimethyl perylimide (Ia q; C.I. Pigment Red 179), represent important
pigments for dyeing varnishes, in particular motor vehicle enamels and
plastics materials.
Various processes for the preparation of dimethyl perylimide (Ia) are
known, these being summarized in DE-A 2,727,484. Thus the preparation of
(Ia) can take place by the reaction of perylene-3,4,9,10-tetracarboxylic
acid diimide (II; referred to below as "perylimide") with methyl chloride
in sodium hydroxide solution under pressure (DE-A 1,272,270), by alkali
metal hydroxide fusion of N-methylnaphthalenecarboxylic acid imide (DE-PS
276,357), or by the reaction of perylene-3,4,9,10-tetracarboxylic acid
dianhydride with aqueous methylamine under pressure (DE-A 2,153,087). Only
in the last-named reaction, which is elaborate, since the dianhydride must
first of all be prepared by saponification of perylimide (II), pigments
can be obtained in tints ranging from pure red to yellowish red, whilst
the first-named reactions give pigments in chestnut tints, which are
subjected to elaborate purification steps such as vatting, alkaline
extraction of the leuco-compound, and reoxidation (DE-A 2,727,484) to
obtain pure red tints.
Furthermore WO-A 96/08537 describes a process for the N-methylation of
organic pigments by reaction with dimethyl carbonate in the presence of
triethylamine and a polar organic solvent such as dimethyl acetamide. In
this reaction, which takes up to 100 h, however, only mixtures of products
having different degrees of methylation are obtained, and these must be
separated. Thus dimethyl perylimide (Ia) is also obtained only in the form
of a chestnut-colored product having a purity of 62%.
It is thus an object of the invention to make dialkyl perylimides (I)
economically available in high purity and good yields.
Accordingly, we have found a process for the preparation of N,N'-di(C.sub.1
-C.sub.4)alkylperylene-3,4,9,10-tetracarboxylic acid diimides (I) by the
reaction of perylene-3,4,9,10-tetracarboxylic acid diimide (II) with a
C.sub.1 -C.sub.4 alkyl halide, wherein the reaction is carried out in a
dipolar-aprotic organic solvent in the presence of an inorganic base.
Suitable dipolar-aprotic solvents for this purpose are, in addition to
sulfoxides and sulfolanes, primarily carboxamides, in particular aliphatic
carboxamides (preferably N,N-di(C.sub.1 -C.sub.4 alkyl)C.sub.1 -C.sub.2
carboxamides), lactams and cyclic and acyclic urea derivatives, and
mixtures thereof. These solvents are preferably used in dried form.
The following are specific examples thereof: dimethyl sulfoxide, sulfolane,
dimethyl formamide, diethyl formamide, dibutyl formamide, dimethyl
acetamide, diethyl acetamide, dibutyl acetamide, N-formylmorpholine,
N-methylpyrrolidone, 1,3'-dimethylimidazolidin-2-one,
1,3'-dimethyltetrahydropyrimidin-2-one, and tetramethyl urea.
For the purposes of the invention, dimethyl formamide and, in particular,
dimethyl acetamide are preferred.
The amount of solvent is not critical and is usually from 10 to 200 moles,
preferably from 40 to 60 moles per mole of perylimide (II).
Suitable inorganic bases are primarily the alkali metal salts (lithium and
preferably sodium and potassium salts) of weak inorganic acids such as
carbonic acid and phosphoric acid, and also mixtures of these salts.
The following can be cited as being particularly suitable examples: sodium
bicarbonate and potassium hydrogen carbonate and also trisodium phosphate
and preferably sodium carbonate and potassium carbonate.
There are normally used, per mole of perylimide (II), from 2 to 10 mol and
preferably from 2 to 5 mol of inorganic base.
Suitable alkylating agents are the alkyl iodides and also, in particular,
the alkyl bromides and, more particularly, the alkyl chlorides, which have
C.sub.1 -C.sub.4 alkyl radicals.
The ethyl and methyl halides are of special significance, preferably ethyl
chloride and more preferably methyl chloride.
From 1 to 20 mol and preferably from 4 to 10 mol of alkyl halide per mole
of perylimide (II) are usually employed.
No surfactants are usually employed in the process of the invention. If,
however, the reaction is to be carried out in the presence of these
agents, then cationic surfactants are primarily suitable such as
ammonium salts of the formula R.sub.4 N.sup.+ X.sup.-, in which the
radicals R denote the same or different alkyl groups (usually C.sub.1
-C.sub.16) and/or aryl groups (usually phenyl or benzyl) and the anions
X.sup.- preferably stand for anions of inorganic acids, such as chloride,
bromide, iodide, hydrogen sulfate, methyl sulfate, perchlorate and
hydroxide, and also for anions of organic acids, such as benzoate, such as
tri(C.sub.1 -C.sub.4 alkyl)phenyl-, tri(C.sub.1 -C.sub.4 alkyl)benzyl-,
di(C.sub.1 -C.sub.4 alkyl)dibenzyl and C.sub.10 -C.sub.16
alkyl-tri(C.sub.1 -C.sub.4 alkyl)ammonium salts;
pyridinium salts of the formula R(C.sub.5 H.sub.5 N).sup.+ X.sup.-, such as
N-C.sub.10 -C.sub.16 alkyl and N-phenyl(C.sub.7 -C.sub.10 alkyl)pyridinium
salts;
phosphonium salts of the formula R.sub.4 P.sup.+ X.sup.-.
The following can be cited as being preferred in the present process: the
phosphonium and, in particular, the ammonium salts.
The following may be cited as specific examples: tetra-n-butylammonium
chloride, bromide, iodide, hydrogen sulfate, and hydroxide,
tetra-n-pentylammonium chloride and bromide, tetra-n-hexylammonium
chloride, bromide, and hydrogen sulfate, trioctylpropylammonium chloride
and bromide, tricaprylmethylammonium chloride, cetyltrimethylammonium
chloride, bromide and methyl sulfate, lauryltrimethylammonium chloride,
lauryltriethylammonium chloride, phenyltrimethylammonium chloride,
phenyltriethylammonium chloride, benzyltrimethylammonium chloride,
bromide, and hydroxide, benzyltriethylammonium chloride and bromide,
benzyltributylammonium chloride and bromide, dibenzyldiethylammonium
chloride, dibenzyldiethylammonium chloride, lauryldimethylbenzylammonium
chloride, laurylpyridinium chloride, cetylpyridinium chloride,
benzylpyridinium chloride, tetraphenylphosphonium chloride,
benzyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide,
tetra-n-butylphosphonium chloride, and tri-n-butylhexadecylphosphonium
bromide.
If surfactants are used, their amounts are then usually from 10 to 50 g and
preferably from 15 to 25 g per kilogram of perylimide (II).
The alkylation reaction of the invention is carried out generally at from
60.degree. to 220.degree. C. and preferably at from 140.degree. to
180.degree. C., and under autogenous pressure (usually from 2 to 20 bar;
boiling of the solvent, liberation of CO.sub.2).
The reaction times are usually from 4 to 12 h and in particular from 5 to 9
h.
From a process engineering aspect the process of the invention is
advantageously carried out as follows: the inorganic base and the
perylimide (II) are suspended in an autoclave in the solvent used, after
purging with nitrogen the alkylating agent is added, which in the case of
the preferred methyl and ethyl chlorides is advantageously effected by
forcing in the gaseous material, and the mixture is heated to the
temperature of reaction with stirring over a period of from approximately
0.5 to 2 h. After stirring over a period of approx. 5 to 10 hours at this
temperature the reaction mixture is cooled and the autoclave is
depressurized.
Purification of the reaction mixture to give the alkyl perylimides (I) can
take place in the usual manner by isolation, by filtration, washing, first
with solvent and then with water, followed by drying.
The process of the invention makes it possible to prepare the alkyl
perylimides (I) in good yields and very high purity in a simple manner.
The alkyl perylimides (I) obtained can be used for dyeing purposes without
further purification immediately following usual pigment enhancement.
The process of the invention is of particular significance regarding the
preparation of dimethyl perylimide (Ia), which is obtained as a red
pigment having a purity of usually better than 95% and having a slight
yellow cast, in the form of needles having a length of approximately 1 to
100 .mu.m.
EXAMPLE
In a stirred autoclave 50 g of perylene-3,4,9,10-tetracarboxylic acid
diimide (II; as 96% strength; calc. As 100%; obtained by alkali metal
fusion of naphthalimide) were introduced into a mixture of 67.5 g of
anhydrous potassium carbonate and 500 g of dimethyl acetamide with
stirring. After purging with nitrogen there were forced in 42 g of methyl
chloride. The reaction mixture was then heated over a period of 1 h to a
temperature of 160.degree. C. (increasing autogenous pressure from 4 to 12
bar), stirred at this temperature over a period of 6 h and then cooled.
Following pressure let-down the product was filtered off, washed first with
dimethyl acetamide and then with water, and dried at 70.degree. C.
There were obtained 52.5 g of
N,N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide (Ia) having a
purity of 96% in the form of readily filterable needles having a length of
from 1 to 100 .mu.m, which is equivalent to a yield of 96%. Pigment
enhancement (milling and recrystallization) gave a brilliant red pigment
having a yellow cast.
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